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Carotenoid


DATA No : VCA0017 INFORMANT : Masayoshi Ito

NAME : (3R,3'R)-3,3'-Dihydroxy-b,b-carotene-4,4'-dione

COMMON NAME: (3R,3'R)-Astaxanthin
SYMBOL:
FORMULA: C40H52O4 MOL.WT (average) : 596.838


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BIOLOGICAL ACTIVITY
Antioxidant activity (Ref. 0092/0093/0215)
Singlet oxygen quenching activity (Ref. 0088/0230/0441)
Immunomodulating action (Ref. 0213)
Chemoprevention of carcinogenesis (Ref. 0218/0219)
PHYSICAL AND CHEMICAL PROPERTIES
MELTING POINT:

BOILING POINT:

REFRACTIVE INDEX:

OPTICAL ROTATION:

DENSITY:

SOLUBILITY:
SPECTRAL DATA
UV SPECTRA:lmax (nm) (e): CHCl 3492 (1920) (Ref. 0010/0077)

IR SPECTRA:nmax(KBr)/cm-1: 3486m (OH), 1664s (conj. CO), 1607m, 1557s (C=C), 1399w, 1390m, 1366w (gem. Dimetyl), 1076s, 1039m (OH) and 969s (CH=CH, trans)
[Spectrum 0003] (Ref. 0010/0077)

NMR SPECTRA:1H-NMR d(500 MHz, CDCl3): 1.21 and 1.32 (each 6H, s, 1, 1'-gem-Me), 1.81 (2H, t, J 13, 2, 2'-Hax), 1.94 (6H, s, 5, 5'-Me), 1.98 and 2.00 (each 6H, s, 9, 9', 13, 13'-Me), 2.16 (2H, dd, J 6 and 13, 2, 2'-Heq), 3.67 (2H, d, J 2, 3, 3'-OH), 4.32 (2H, ddd, J 2, 6 and13, 3, 3'-H) and 6.20-6.70 (14H, m, olefinic-H) (Ref. 0068/0077)

MASS SPECTRA:m/z: 596 (M), (M-16), (M-16-16), (M-79), (M-92), (M-106), (M-92-16), (M-106-16), (M-154), (M-167), (M-207), (M-219), (M-233) (Ref. 0058/0077)

OTHER SPECTRA:CD data in EPA solution (25degC): De 240 (+20.0), 252 (0), 270 (-20.0), 284 (0), 314 (+34.0), 355 (0), 372 (-3.0) (Ref. 0421)
CHROMATOGRAM DATA
TLC (Kieselgel 60 Merck, CH2Cl2-acetone-formic acid 95:5:3) Rf = 0.3 --- (3S,3'S)-astaxanthin (Ref. 0010)
HPLC (column: Sumipax OA-2000 (10mm) 0.4times25 cm, eluent: hexane-CH2Cl2-EtOH 48:16:0.6, flow: 0.8 ml/min) tR = ca. 57 min (3R,3'R), ca. 60 min (meso), ca. 64 min (3S,3'S)
[Chromatogram 0004] (Ref. 0069/0070/0210)
HPLC (column: LiChrosorb SI 60 (5 mm) 0.32times50 cm, eluent: hexane-ethyl acetate-acetonitrile 88:10:2, flow: 0.8 ml/min) tR = ca. 42 min (diacetate of all-E isomer)
[Chromatogram 0005] --- racemic astaxanthin (Ref. 0071)
HPLC (columun: TSK gel ODS-80Ts (Tosoh) 0.46times15 cm, eluent and flow: 1.0 ml/min, H2O-MeOH 5:95 for 5 min, follwed by 5 min-linear gradient MeOH-THF 7:3, and then MeOH-THF 7:3 for 5 min) b-carotene, echinenone, b-cryptoxanthin, 3-hydroxy-echinenone, cantaxanthin, 3'-hydroxy-echinenone, cis-adonixanthin, adonirubin, adonixanthin and astaxanthin were separated. tR = 6.30 min for astaxanthin (Ref. 0208).
Separation of (3S,3'S), (3S,3'R) and (3R,3'R) astaxanthin by HPLC on a Pirkle covalent L-leucine column (Ref. 1164).
SOURCE
Phaffia rhodozyma (Xanthophyllomyces dendrorhous) (yeast) (Ref. 0425)
Homarus gammarus (Lobster) (Ref. 0418)
Salmo salar, Oncorhynchus (salmon) (Ref. 0419)
Asterias rubens (starfish) (Ref. 0420)
Shrimps and lobsters (Ref. 0421)
Euphausia superba (antarctic krill) (Ref. 0422)
Asterina pectinifera, Asterias amurensis (starfish) (Ref. 0423)
Watasenia scintilans, Sepia modokai, Sepia officinales (cuttlefish) (Ref. 0424)
Octopus vulgaris, Octopus ocellatus, Octopus minor (octopus) (Ref. 0424)
CHEMICAL SYNTHESIS
The Wittig condensation of C10-dialdehyde with 2 equiv. of C15-phosphonium salt and subsequent thermal isomerization afforded astaxanthin.
(3S,3'S)- and (3R,3'R)-Astaxanthin --- Enantiomeric chiral blocks of C15-phosphonium salts were synthesized via three different routes. (Ref. 0012/0016)
(3S,3'S)- and (3R,3'R)-Astaxanthin --- C15-Phosphonium salts were prepared from enantiomeric 3-acetoxy-4-oxo-b-ionones obtained by separation of the corresponding diastereomeric camphanates and by microbial resolution. (Ref. 0015/0073)
METABOLISM
Only Phaffia rhodozyma (Xanthophyllomyces dendrorhous) (yeast) synthesizes (3R,3'R)-astaxanthin, while other organisms, such as bacteria and green algae, synthesize (3S,3'S)-form (Ref. 0425).
b-Ionone, an end ring analog of b-carotene, inhibits astaxanthin synthesis from b-carotene in the Phaffia rhodozyma (Ref. 1267).
GENETIC INFORMATION

NOTE
Almost the same stereochemical composition in astaxanthin, its monoester and its diester in krill are found: 62-71% (3R,3'R)-, 11-14% (3R,3'S; meso)- and 17-26% (3S,3'S)-astaxanthin (Ref. 0422). Those in Euphausia, Thysanoessa, Calanus, Acanthephyra and Cancer (Crustaceans) are also reported (Ref. 1257).
Semi-empirical molecular orbital calculations using AM1 Hamiltonian (MNDO-AM1 method) were performed in order to predict their stable structures (Ref. 1337).
REFERENCES
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